CN104610173A - Recycling production process for nigrosine - Google Patents
Recycling production process for nigrosine Download PDFInfo
- Publication number
- CN104610173A CN104610173A CN201510015951.0A CN201510015951A CN104610173A CN 104610173 A CN104610173 A CN 104610173A CN 201510015951 A CN201510015951 A CN 201510015951A CN 104610173 A CN104610173 A CN 104610173A
- Authority
- CN
- China
- Prior art keywords
- aniline
- condenser
- water
- tower
- nigrosine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
- C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
- C07D241/46—Phenazines
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/86—Separation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
- C07C211/45—Monoamines
- C07C211/46—Aniline
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B17/00—Azine dyes
- C09B17/02—Azine dyes of the benzene series
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
- F25B15/00—Sorption machines, plants or systems, operating continuously, e.g. absorption type
- F25B15/02—Sorption machines, plants or systems, operating continuously, e.g. absorption type without inert gas
- F25B15/06—Sorption machines, plants or systems, operating continuously, e.g. absorption type without inert gas the refrigerant being water vapour evaporated from a salt solution, e.g. lithium bromide
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
- F25B27/00—Machines, plants or systems, using particular sources of energy
- F25B27/02—Machines, plants or systems, using particular sources of energy using waste heat, e.g. from internal-combustion engines
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A30/00—Adapting or protecting infrastructure or their operation
- Y02A30/27—Relating to heating, ventilation or air conditioning [HVAC] technologies
- Y02A30/274—Relating to heating, ventilation or air conditioning [HVAC] technologies using waste energy, e.g. from internal combustion engine
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B30/00—Energy efficient heating, ventilation or air conditioning [HVAC]
- Y02B30/62—Absorption based systems
- Y02B30/625—Absorption based systems combined with heat or power generation [CHP], e.g. trigeneration
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- General Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Combustion & Propulsion (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
Abstract
The invention relates to a recycling production process for nigrosine. The recycling production process comprises the following steps: 1) condensing aniline and nitrobenzene in a condensation reaction kettle to obtain a nigrosine product containing excessive aniline; 2) acidifying the nigrosine product in an acidification reaction kettle, and centrifuging through a centrifugal machine to obtain nigrosine and aniline-containing wastewater; 3) mixing alkaline liquor and the aniline-containing wastewater through a static mixer to obtain a mixture, feeding the mixture at the tower-top of a rectifying tower, introducing steam from the tower-bottom, performing steam stripping on the aniline-containing wastewater, and processing in a sewage plant after exchanging heat of the tower-bottom wastewater through a heat exchanger; 4) introducing a gas-phase mixture of tower-top aniline water into a lithium bromide set condenser to condense; introducing 12-DEGC circulating water into the lithium bromide set condenser to form 7-DEG C circulating water for refrigerating, and converting into 12-DEG C circulating water for use after refrigerating; 5) changing the condensed gas-phase mixture into a liquid-phase mixture, condensing through the condenser, layering through a layering device, and performing the operation of step 3) on a little aniline in an upper-layer water phase in a circulating manner, and performing operation of the step 1) on lower-layer aniline phase in the circulating manner.
Description
Technical field
The present invention relates to technical field of dye, specifically, relate to a kind of cycle production process of nigrosine.
Background technology
Nigrosine is a kind of chemistry dyestuff, and its strong coloring force, dispersiveness is low, light absorptive good, color steadiness is high, and therefore to can be used for Plastic Resin painted for nigrosine, ink colorant, wood decoration technique is painted, leather, cotton, fiber crops dyeing and cover with paint, lacquer, colour wash, etc., the fields such as the painted and pigment coloration of metal products.
The technique preparing nigrosine is at present generally, by aniline and oil of mirbane after ferric trichloride catalytic condensation through acidifying, washing, filtration, that drying obtains alcohol soluble aniline is black; Carry out sulfonation, segregation, washing, neutralization, drying by black for the alcohol soluble aniline obtained, prepare water soluble aniline black; This method production technique cycle of preparing water soluble aniline black is long, energy consumption is high.Application number be 200910009273.1 Chinese patent disclose a kind of method preparing water soluble aniline black, detailed process is: aniline and oil of mirbane are carried out condensation reaction under the catalysis of iron trichloride; The reaction product obtained is naturally cooled to 25 DEG C; Put in sulfuric acid after cooled reaction product is pulverized and carry out sulfonation reaction; The sulfonation reaction product obtained is emanated in cold water; Sulfonation reaction product after segregation is carried out solid-liquid separation and washing, then carries out processed; Material sodium hydroxide after dehydration or sodium carbonate are carried out neutralization reaction; The neutralization reaction product obtained is carried out drying, obtains emboliform water soluble aniline black.This method preparing water soluble aniline black avoid prepare alcohol soluble aniline black time acidifying, washing, filtration, dry four loaded down with trivial details processing steps, the process cycle producing nigrosine is short, cost is lower.
Although what the preparation method of the nigrosine that prior art provides can be quick, easy prepares nigrosine, but in the process preparing nigrosine, produce a large amount of aniline solid waste containing iron ion, this aniline solid waste is directly discharged in environment, causes the pollution of environment and wastes a large amount of iron resourcess.
For this reason, application number be 201410165499.1 Chinese patent disclose a kind of aniline solid waste that utilizes and produce the method for nigrosine, comprise the following steps: 1) aniline solid waste, acidic cpd and oxygenant are carried out oxidizing reaction, obtain liquor ferri trichloridi, described aniline solid waste comprises oxyhydroxide and the nigrosine of iron; 2) carry out underpressure distillation by after described liquor ferri trichloridi and aniline mixing, obtain mixture; 3) described mixture and oil of mirbane are carried out condensation reaction, obtain nigrosine.Although aniline solid waste is converted into liquor ferri trichloridi in order to prepare nigrosine by the method, avoids aniline solid waste and directly discharge the problem of environmental pollution caused.But utilizing rectifying tower to extract in aniline process, rectifying tower top can produce aniline steam and the water vapour of uniform flow, in per hour, the aniline steam of even generation 5310kg per hour and water vapour, this part gas mixture phase component contains a large amount of gas-phase potential heats, and its top gaseous phase latent heat is calculated as follows:
Known: 100 DEG C of water vapor enthalpys are: 2677KJ/Kg; The enthalpy of 100 DEG C of water is: 417.5KJ/Kg; Aniline enthalpy of vaporization is: 487.335KJ/Kg.
The gas-phase potential heat of rectifying tower tower top generation per hour is:
The Q always latent+Q water of latent=Q aniline dives
Q water is dived=0.84 × 5310 × (2677-417.5)=10078274KJ
Q aniline is dived=0.16 × 6000 × 487.335=414040KJ
Q is latent=10078274+414040=10492314KJ always
I.e. overhead vapours phase transformation generation latent heat per hour 10492314KJ, amounts to 249.8 ten thousand kilocalories.
Visible, containing a large amount of gas-phase potential heats in the gas mixture phase component of the aniline steam that rectifying tower tower top produces and water vapour, needing to carry out cooling process could aniline recovery.Ordinary method utilizes circulating water cooling or atmospheric condenser cooling, as Fig. 1 discloses a kind of schematic flow sheet of aniline distillation recovery device, waste water in storage tank 1 is containing aniline about 4%, the tower top of rectifying tower 3 is sent into after feed preheater 2 preheating, live steam directly enters at the bottom of the tower of rectifying tower 3, carry out stripping to containing aniline waste water, waste water at the bottom of tower is discharged after reclaiming preheating by feed preheater 2, send biochemical processing process.Tower top high concentration aniline gas-vapor mix condenses to through condenser 4 decker 5 that about 40 DEG C enter aniline, water, and upper strata aqueous phase contains a small amount of aniline, and send storage tank 1 back to and circulate distillation to reclaim aniline wherein, lower floor's aniline can recycle mutually.So not only can waste a large amount of recirculated water, and this partial heat also can not get effective utilization, thus cause the waste of this partial heat, financial loss is larger.
The recovery of aniline " in the alcohol soluble nigrosine factory effluent " [Wang Shouheng, Deng. the recovery [J] of aniline in alcohol soluble nigrosine factory effluent, 2009, 30 (3): 48-50] have also been devised a kind of device of improvement, as shown in Figure 2, squeeze in line mixer containing the aniline waste water lift pump 11 that contains of about 4%, add caustic soda neutralization and be adjusted to certain pH value, the storage tank 1 entering neutralizer after removal iron trichloride is filtered through manganese sand filter 12, in storage tank 1 aniline water aniline water pump boosting and after the shell side of feed preheater 2 is preheating to 90 DEG C by overhead vapours, send into the charging of rectifying tower 3 tower top.From rectifying tower 3 tower top steam out and wastewater feed heat exchange, uncooled steam enters after air cooler 15 is cooled to 60 DEG C, be mixed into condenser 4 with the condensation liquid phase of feed preheater 2 to continue to be cooled to about 40 DEG C, material after process send the decker 5 of aniline, water, equally, upper strata aqueous phase is sent storage tank 1 back to and is circulated distillation to reclaim aniline wherein, and lower floor's aniline is as raw material recycle in reaction process.At the bottom of the tower of rectifying tower 3, waste water first delivers to flash tank 14, then utilizes saturated waste water in injector 13 pairs of flash tanks 14 to carry out vacuum flashing, to reclaim heat, discharges after reclaiming preheating again.But utilize air cooler condensation not make full use of the gas-phase potential heat of tower top aniline steam and water vapour, thus cause and waste a large amount of heats.
In view of this, special proposition the present invention.
Summary of the invention
The object of the present invention is to provide a kind of cycle production process of nigrosine, the method not only effectively prevent directly discharges containing aniline waste water the problem of environmental pollution caused, also effectively utilize the aniline steam of rectifying tower tower top and the gas-phase potential heat of water vapor, low-pressure steam is utilized to drive lithium bromide chiller condenser, produce 7 DEG C of cold water to freeze for other workshops, the heat of rectifying tower tower top is comprehensively effectively utilized, and economic benefit is obvious.
For realizing object of the present invention, the present invention adopts following technical scheme:
A cycle production process for nigrosine, wherein, described cycle production process comprises the steps: 1) aniline and oil of mirbane are carried out condensation reaction under catalyzer existent condition in condensation reaction still, obtain the nigrosine product containing excessive aniline;
2) under hydrochloric acid and hot water existent condition, by step 1) gained in acidification reaction still, carry out acidification reaction containing the nigrosine product of excessive aniline, then products obtained therefrom is obtained nigrosine product by centrifuge and containing aniline waste water;
3) by alkali lye with after being mixed by static mixer containing aniline waste water, send into rectifying tower tower top, steam directly enters at the bottom of rectifying tower simultaneously, carries out stripping to containing aniline waste water, and the waste water produced at the bottom of rectifying tower after stripping is decontaminated water factory and office reason after interchanger heat exchange;
4) aniline of rectifying tower tower top generation and the gas phase mixture of water enter lithium bromide chiller condenser condenses; 12 DEG C of recirculated waters enter lithium bromide chiller condenser simultaneously, the gas-phase potential heat produced by the gas phase mixture of aniline and water drives lithium bromide chiller condenser to form 7 DEG C of recirculated waters for refrigeration, is converted into 12 DEG C of recirculated waters and enters lithium bromide chiller condenser again and recycle after use of freezing;
5) gas phase mixture through lithium bromide chiller condenser condenses becomes liquid phase mixture, condensation is carried out successively by the first condenser and the second condenser, then enter decker and carry out layering, upper strata aqueous phase contains a small amount of aniline, send back to static mixer circulation carry out step 3) operation; Lower floor's aniline to return in condensation reaction still circulation as the raw material of synthesis nigrosine and carry out step 1) operation.
At present, containing a large amount of gas-phase potential heats in the gas mixture phase component of the aniline steam that rectifying tower tower top produces and water vapor, needing to carry out cooling process could aniline recovery.Ordinary method utilizes circulating water cooling or atmospheric condenser cooling, and so not only can waste a large amount of recirculated water, and this partial heat also can not get effective utilization, thus cause the waste of this partial heat, financial loss is larger.
The present invention effectively utilizes the aniline steam of rectifying tower top and the gas-phase potential heat of water vapor, low-pressure steam is utilized to drive lithium bromide chiller condenser, produce 7 degree of cold water to freeze for each workshop, the water of 12 degree is converted into after each workshop reacting kettle jacketing or interchanger heat exchange, the water cycle of generation 7 degree after lithium bromide chiller is driven to use through low-pressure steam again, the heat of rectifying tower tower top is comprehensively effectively utilized, and economic benefit is obvious.Meanwhile, the raw material that the aniline of recovery can be used as nigrosine returns production technique recycle.
In cycle production process of the present invention, wherein, step 3) in be 3 ~ 8% containing the mass percentage content of the Aniline of aniline, preferably 4%; The mass percentage content of the Aniline produced at the bottom of tower is < 300ppm.
Step 4) in the temperature of gas phase mixture of aniline and water be 102 ~ 104 DEG C.
Step 5) in the temperature of liquid phase mixture be 95 ~ 100 DEG C.
Step 5) described in liquid phase mixture behind the first condenser and the second condenser condenses to 20 ~ 25 DEG C, enter decker successively and carry out layering.
Step 3) in lower floor aniline mutually in the mass percentage content of aniline be 94 ~ 98%.
Described lithium bromide chiller condenser, the first described condenser and the second condenser are connected with cooling water supply pipe and CWR respectively.
The downside of described rectifying tower is provided with condensation-water drain.
In above-mentioned cycle production process, step 1) in the mass ratio of aniline and oil of mirbane be 4 ~ 6:1, the temperature of condensation reaction is 160 ~ 200 DEG C, and the time of condensation reaction is 4 ~ 6 hours, and described catalyzer is FeCl
3.
In above-mentioned cycle production process, step 2) described in the temperature of reaction of acidification reaction be 90 ~ 100 DEG C, the time of acidification reaction is 1 ~ 2 hour.
In the present invention, the steam condensate that steam produces after heat exchange at the bottom of rectifying tower flows out from this condensation-water drain.
Adopt the cycle production process economic benefit of nigrosine provided by the present invention obvious, by rectifying tower top generation per hour 5310Kg low-pressure steam, replacing 0.6MPa steam driven lithium bromide chiller to produce 7 DEG C of cool water quantities is 500m
3/ h, supply workshop refrigeration needs.Steam expense per ton is by 200 yuan of calculating, and the whole year can steam saving expense about 7,650,000.
The cycle production process of nigrosine provided by the present invention is realized by the circulation device for the production of nigrosine provided by the present invention.
The described circulation device for the production of nigrosine, comprises condensation reaction still, acidification reaction still, rectifying tower, condenser and decker, wherein, is connected with whizzer between described acidification reaction still and rectifying tower; Be connected with lithium bromide chiller condenser between described rectifying tower and described condenser, described lithium bromide chiller condenser is provided with recirculated water entrance and circulating water outlet.
At present, containing a large amount of gas-phase potential heats in the gas mixture phase component of the aniline steam that rectifying tower tower top produces and water vapor, needing to carry out cooling process could aniline recovery.Ordinary method utilizes circulating water cooling or atmospheric condenser cooling, and so not only can waste a large amount of recirculated water, and this partial heat also can not get effective utilization, thus cause the waste of this partial heat, financial loss is larger.
The present invention arranges whizzer at described acidification reaction still with being connected between rectifying tower, Working environment can be made to be that fully-closed operates by open type operation adjustment, effectively prevent the volatilization of material, protect environment; Improve the operating environment of worker.Simultaneously, the present invention effectively utilizes the aniline steam of rectifying tower top and the gas-phase potential heat of water vapor, low-pressure steam is utilized to drive lithium bromide chiller condenser, produce 7 DEG C of water to freeze for each workshop, 12 DEG C of water are converted into after each workshop reacting kettle jacketing or interchanger heat exchange, produce 7 DEG C of water cycles after entering lithium bromide chiller condenser condenses again to use, the heat of rectifying tower tower top is comprehensively effectively utilized, and economic benefit is obvious.Meanwhile, the raw material that the aniline reclaimed after rectifying tower stripping, lithium bromide chiller condenser condenses, condenser condenses and decker layering containing aniline waste water can be used as nigrosine returns production technique recycle.
In order to improve condensation effect further, condenser of the present invention comprises the first condenser and the second condenser, and the first described condenser and the second condenser are connected in turn between described lithium bromide chiller condenser and decker.
Further, described lithium bromide chiller condenser is provided with aniline steam entry and aniline water out; Described aniline steam entry is connected by the tower top of pipeline with described rectifying tower; Described aniline water out is connected with the first described condenser by pipeline.
Preferably, the upside of described rectifying tower is also connected with static mixer.
Further, one end of described static mixer is provided with alkali liquor inlet and contains aniline waste water entrance, and the other end is connected with the upside of described rectifying tower.
Initial pH value containing the mother liquor of aniline waste water is acid, aniline exists with the form of hydrochloride, by connecting in the upside of rectifying tower, a static mixer is set, mother liquor containing aniline waste water is mixed from entering static mixer containing aniline waste water entrance, in static mixer, add liquid caustic soda mixing by alkali liquor inlet to neutralize simultaneously, after neutralization, aniline is converted into aniline by the form of anilinechloride, thus is convenient to rectifying.
In the present invention, the downside of described rectifying tower is provided with steam-in and condensation-water drain.
The steam-in of live steam on the downside of rectifying tower directly enters, and carry out stripping to containing aniline waste water, the steam condensate produced after stripping heat exchange flows out from described condensation-water drain.
In the present invention, described lithium bromide chiller condenser, the first described condenser and the second condenser are connected with cooling water supply pipe and CWR respectively.
As a preferred embodiment of the present invention, at the bottom of the tower of rectifying tower of the present invention, be connected with interchanger.
Containing heat waste water out at the bottom of rectifying tower, if directly send sewage work to process, the waste of this part heat will be caused.The present invention connects and arranges an interchanger at the bottom of rectifying tower, and waste water at the bottom of such tower enters sewage work's process after collecting heat by interchanger heat exchange again, thus avoids the waste of waste water heat at the bottom of tower.
Compared with prior art, tool of the present invention has the following advantages:
(1) cycle production process of nigrosine provided by the present invention effectively can process the waste water in aniline black dyestuffs production process, realize the resource utilization of pollutent and the cleaner production of nigrosine, the removal of aniline can reduce the murder by poisoning to biochemical wastewater treatment, provides premise for sewage farm realizes qualified discharge; Meanwhile, the raw material that the aniline of recovery can be used as nigrosine returns production technique recycle;
(2) cycle production process of nigrosine provided by the present invention effectively utilizes the aniline steam of rectifying tower top and the gas-phase potential heat of water vapour, low-pressure steam is utilized to drive lithium bromide chiller condenser, produce 7 degree of cold water to freeze for each workshop, the water of 12 degree is converted into after each workshop reacting kettle jacketing or interchanger heat exchange, the water cycle of generation 7 degree after lithium bromide chiller is driven to use through low-pressure steam again, the heat of rectifying tower tower top is comprehensively effectively utilized, and economic benefit is obvious.
Accompanying drawing explanation
Fig. 1 is the structural representation of the aniline distillation recovery device of prior art;
Fig. 2 is the structural representation of the aniline distillation recovery device that prior art is improved;
Fig. 3 is the schematic diagram of the cycle production process of nigrosine provided by the present invention;
Wherein, in accompanying drawing, each component names is as follows:
1---storage tank, 2---feed preheater, 3---rectifying tower, 4---condenser, 41---the first condenser, 42---the second condenser, 5---decker, 6---lithium bromide chiller condenser, 7---static mixer, 8---interchanger, 9---cooling water supply pipe, 10---CWR, 11---lift pump, 12---manganese sand filter, 13---injector, 14---flash tank, 15---air cooler, 16---condensation reaction still, 17---acidification reaction still, 18---whizzer.
Embodiment
Be below the specific embodiment of the present invention, described embodiment is to further describe the present invention, instead of restriction the present invention.
Embodiment 1
1) aniline and oil of mirbane are carried out condensation reaction under catalyzer existent condition in condensation reaction still 16, obtain the nigrosine product containing excessive aniline, wherein the mass ratio of aniline and oil of mirbane is 4:1, the temperature of condensation reaction is 160 DEG C, the time of condensation reaction is 4 hours, and described catalyzer is FeCl
3;
2) under hydrochloric acid and hot water existent condition, by step 1) gained in acidification reaction still 17, carry out acidification reaction containing the nigrosine product of excessive aniline, then products obtained therefrom is obtained nigrosine product by whizzer 18 is centrifugal and contains aniline waste water, the temperature of reaction of wherein said acidification reaction is 90 DEG C, and the time of acidification reaction is 1 hour;
3) as shown in Figure 3, by alkali lye and aniline content be 4wt% containing after aniline waste water mixed by static mixer 7, send into rectifying tower 3 tower top, steam directly enters at the bottom of rectifying tower 3 tower simultaneously, carry out stripping to containing aniline waste water, the waste water produced at the bottom of rectifying tower 3 tower after stripping is decontaminated water factory and office reason after interchanger 8 heat exchange; Wherein, the mass percentage content of the Aniline produced at the bottom of tower is less than 300ppm, and the consumption of alkali lye is 1075Kg/h;
4) temperature that rectifying tower 3 tower top produces is that the aniline of 102 DEG C and the gas phase mixture of water enter lithium bromide chiller condenser 6 condensation; 12 DEG C of recirculated waters enter lithium bromide chiller condenser 6 simultaneously, the gas-phase potential heat produced by the gas phase mixture of aniline and water drives lithium bromide chiller condenser 6 to form 7 DEG C of recirculated waters for refrigeration, is converted into 12 DEG C of recirculated waters and enters lithium bromide chiller condenser 6 again and recycle after use of freezing;
5) liquid phase mixture of 95 DEG C is become through the gas phase mixture of lithium bromide chiller condenser 6 condensation, condensation is carried out successively by the first condenser 41 and the second condenser 42, enter decker 5 after being condensed to 20 DEG C and carry out layering, upper strata aqueous phase contains a small amount of aniline, send back to static mixer 7 circulation carry out step 3) operation; Lower floor's aniline to return in condensation reaction still 16 circulation as the raw material of synthesis nigrosine and carry out step 1) operation; Wherein lower floor's aniline mutually in the content of aniline be 94wt%.
Described lithium bromide chiller condenser 6, the first described condenser 41 and the second condenser 42 are connected with cooling water supply pipe 9 and CWR 10 respectively.
Embodiment 2
1) aniline and oil of mirbane are carried out condensation reaction under catalyzer existent condition in condensation reaction still 16, obtain the nigrosine product containing excessive aniline, wherein the mass ratio of aniline and oil of mirbane is 6:1, the temperature of condensation reaction is 200 DEG C, the time of condensation reaction is 6 hours, and described catalyzer is FeCl
3;
2) under hydrochloric acid and hot water existent condition, by step 1) gained in acidification reaction still 17, carry out acidification reaction containing the nigrosine product of excessive aniline, then products obtained therefrom is obtained nigrosine product by whizzer 18 is centrifugal and contains aniline waste water, the temperature of reaction of wherein said acidification reaction is 100 DEG C, and the time of acidification reaction is 2 hours;
3) as shown in Figure 3, by alkali lye and aniline content be 3wt% containing after aniline waste water mixed by static mixer 7, send into rectifying tower 3 tower top, steam directly enters at the bottom of rectifying tower 3 tower simultaneously, carry out stripping to containing aniline waste water, the waste water produced at the bottom of rectifying tower 3 tower after stripping is decontaminated water factory and office reason after interchanger 8 heat exchange; Wherein, the mass percentage content of the Aniline produced at the bottom of tower is less than 300ppm, and the consumption of alkali lye is 1075Kg/h;
4) temperature that rectifying tower 3 tower top produces is that the aniline of 104 DEG C and the gas phase mixture of water enter lithium bromide chiller condenser 6 condensation; 12 DEG C of recirculated waters enter lithium bromide chiller condenser 6 simultaneously, the gas-phase potential heat produced by the gas phase mixture of aniline and water drives lithium bromide chiller condenser 6 to form 7 DEG C of recirculated waters for refrigeration, is converted into 12 DEG C of recirculated waters and enters lithium bromide chiller condenser 6 again and recycle after use of freezing;
5) liquid phase mixture of 100 DEG C is become through the gas phase mixture of lithium bromide chiller condenser 6 condensation, condensation is carried out successively by the first condenser 41 and the second condenser 42, enter decker 5 after being condensed to 25 DEG C and carry out layering, upper strata aqueous phase contains a small amount of aniline, send back to static mixer 7 circulation carry out step 3) operation; Lower floor's aniline returns production technique recycle as the raw material of synthesis nigrosine; Wherein lower floor's aniline mutually in the content of aniline be 98wt%.
Described lithium bromide chiller condenser 6, the first described condenser 41 and the second condenser 42 are connected with cooling water supply pipe 9 and CWR 10 respectively.
Embodiment 3
1) aniline and oil of mirbane are carried out condensation reaction under catalyzer existent condition in condensation reaction still 16, obtain the nigrosine product containing excessive aniline, wherein the mass ratio of aniline and oil of mirbane is 5:1, the temperature of condensation reaction is 180 DEG C, the time of condensation reaction is 5 hours, and described catalyzer is FeCl
3;
2) under hydrochloric acid and hot water existent condition, by step 1) gained in acidification reaction still 17, carry out acidification reaction containing the nigrosine product of excessive aniline, then products obtained therefrom is obtained nigrosine product by whizzer 18 is centrifugal and contains aniline waste water, the temperature of reaction of wherein said acidification reaction is 95 DEG C, and the time of acidification reaction is 1.5 hours;
3) as shown in Figure 3, by alkali lye and aniline content be 8wt% containing after aniline waste water mixed by static mixer 7, send into rectifying tower 3 tower top, steam directly enters at the bottom of rectifying tower 3 tower simultaneously, carry out stripping to containing aniline waste water, the waste water produced at the bottom of rectifying tower 3 tower after stripping is decontaminated water factory and office reason after interchanger 8 heat exchange; Wherein, the mass percentage content of the Aniline produced at the bottom of tower is less than 300ppm, and the consumption of alkali lye is 1075Kg/h;
4) temperature that rectifying tower 3 tower top produces is that the aniline of 103 DEG C and the gas phase mixture of water enter lithium bromide chiller condenser 6 condensation; 12 DEG C of recirculated waters enter lithium bromide chiller condenser 6 simultaneously, the gas-phase potential heat produced by the gas phase mixture of aniline and water drives lithium bromide chiller condenser 6 to form 7 DEG C of recirculated waters for refrigeration, is converted into 12 DEG C of recirculated waters and enters lithium bromide chiller condenser 6 again and recycle after use of freezing;
5) liquid phase mixture of 98 DEG C is become through the gas phase mixture of lithium bromide chiller condenser 6 condensation, condensation is carried out successively by the first condenser 41 and the second condenser 42, enter decker 5 after being condensed to 23 DEG C and carry out layering, upper strata aqueous phase contains a small amount of aniline, send back to static mixer 7 circulation carry out step 3) operation; Lower floor's aniline to return in condensation reaction still 16 circulation as the raw material of synthesis nigrosine and carry out step 1) operation; Wherein lower floor's aniline mutually in the content of aniline be 96wt%.
Described lithium bromide chiller condenser 6, the first described condenser 41 and the second condenser 42 are connected with cooling water supply pipe 9 and CWR 10 respectively.
Embodiment 4
1) aniline and oil of mirbane are carried out condensation reaction under catalyzer existent condition in condensation reaction still 16, obtain the nigrosine product containing excessive aniline, wherein the mass ratio of aniline and oil of mirbane is 5:1, the temperature of condensation reaction is 190 DEG C, the time of condensation reaction is 5.5 hours, and described catalyzer is FeCl
3;
2) under hydrochloric acid and hot water existent condition, by step 1) gained in acidification reaction still 17, carry out acidification reaction containing the nigrosine product of excessive aniline, then products obtained therefrom is obtained nigrosine product by whizzer 18 is centrifugal and contains aniline waste water, the temperature of reaction of wherein said acidification reaction is 98 DEG C, and the time of acidification reaction is 1.8 hours;
3) as shown in Figure 3, by alkali lye and aniline content be 5wt% containing after aniline waste water mixed by static mixer 7, send into rectifying tower 3 tower top, steam directly enters at the bottom of rectifying tower 3 tower simultaneously, carry out stripping to containing aniline waste water, the waste water produced at the bottom of rectifying tower 3 tower after stripping is decontaminated water factory and office reason after interchanger 8 heat exchange; Wherein, the mass percentage content of the Aniline produced at the bottom of tower is less than 300ppm, and the consumption of alkali lye is 1075Kg/h;
4) temperature that rectifying tower 3 tower top produces is that the aniline of 102 DEG C and the gas phase mixture of water enter lithium bromide chiller condenser 6 condensation; 12 DEG C of recirculated waters enter lithium bromide chiller condenser 6 simultaneously, the gas-phase potential heat produced by the gas phase mixture of aniline and water drives lithium bromide chiller condenser 6 to form 7 DEG C of recirculated waters for refrigeration, is converted into 12 DEG C of recirculated waters and enters lithium bromide chiller condenser 6 again and recycle after use of freezing;
5) liquid phase mixture of 96 DEG C is become through the gas phase mixture of lithium bromide chiller condenser 6 condensation, condensation is carried out successively by the first condenser 41 and the second condenser 42, enter decker 5 after being condensed to 20 DEG C and carry out layering, upper strata aqueous phase contains a small amount of aniline, send back to static mixer 7 circulation carry out step 3) operation; Lower floor's aniline to return in condensation reaction still 16 circulation as the raw material of synthesis nigrosine and carry out step 1) operation; Wherein lower floor's aniline mutually in the content of aniline be 97wt%.
Described lithium bromide chiller condenser 6, the first described condenser 41 and the second condenser 42 are connected with cooling water supply pipe 9 and CWR 10 respectively.
Embodiment 5
This embodiment arranges a condensation-water drain in the downside of described rectifying tower further on the basis of embodiment 1, embodiment 2, embodiment 3 or embodiment 4.The steam condensate produced after being convenient to steam heat exchange at the bottom of the tower of rectifying tower 3 flows out from this condensation-water drain.
The cycle production process of the nigrosine described in above-described embodiment is realized by the circulation device for the production of nigrosine provided by the present invention.
The described circulation device for the production of nigrosine, as shown in Figure 3, comprises condensation reaction still 16, acidification reaction still 17, rectifying tower 3, condenser 4 and decker 5, wherein, is connected with whizzer 18 between described acidification reaction still 17 and rectifying tower 3; Be connected with lithium bromide chiller condenser 6 between described rectifying tower 3 and described condenser 4, described lithium bromide chiller condenser 6 is provided with recirculated water entrance and circulating water outlet.
The present invention arranges whizzer 18 at described acidification reaction still 17 with being connected between rectifying tower 3, Working environment can be made to be that fully-closed operates by open type operation adjustment, effectively prevent the volatilization of material, protect environment; Improve the operating environment of worker.Simultaneously, the present invention effectively utilizes the aniline steam of rectifying tower 3 tower top and the gas-phase potential heat of water vapor, low-pressure steam is utilized to drive lithium bromide chiller condenser 6, produce 7 DEG C of water to freeze for each workshop, 12 DEG C of water are converted into after each workshop reacting kettle jacketing or interchanger heat exchange, produce 7 DEG C of water cycles after entering lithium bromide chiller condenser 6 condensation again to use, the heat of rectifying tower 3 tower top is comprehensively effectively utilized, and economic benefit is obvious.Meanwhile, the raw material that the aniline reclaimed after rectifying tower 3 stripping, lithium bromide chiller condenser 6 condensation, condenser 4 condensation and decker 5 layering containing aniline waste water can be used as nigrosine returns production technique recycle.
In order to improve condensation effect further, condenser 4 of the present invention comprises the first condenser 41 and the second condenser 42, and the first described condenser 41 and the second condenser 42 are connected in turn between described lithium bromide chiller condenser 6 and decker 5.
Described lithium bromide chiller condenser 6 is provided with aniline steam entry and aniline water out; Described aniline steam entry is connected by the tower top of pipeline with described rectifying tower 3; Described aniline water out is connected with the first described condenser 41 by pipeline.
The upside of described rectifying tower 3 is connected with static mixer 7.
One end of described static mixer 7 is provided with alkali liquor inlet and containing aniline waste water entrance, the other end is connected with the upside of described rectifying tower 3.
Initial pH value containing the mother liquor of aniline waste water is acid, aniline exists with the form of hydrochloride, by connecting in the upside of rectifying tower 3, a static mixer 7 is set, the mother liquor containing aniline waste water is made to enter static mixer 7 from containing aniline waste water entrance, in static mixer 7, add liquid caustic soda mixing by alkali liquor inlet to neutralize simultaneously, after neutralization, aniline is converted into aniline by the form of anilinechloride, thus is convenient to rectifying.
The downside of described rectifying tower 3 is provided with steam-in and condensation-water drain.
The steam-in of live steam on the downside of rectifying tower 3 directly enters, and carry out stripping to containing aniline waste water, the steam condensate produced after stripping heat exchange flows out from described condensation-water drain.
Described lithium bromide chiller condenser 6, the first described condenser 41 and the second condenser 42 are connected with cooling water supply pipe 9 and CWR 10 respectively.
Comparative example
The method of method of the present invention and prior art contrasted, wherein old device is the device of Fig. 1, and the device of improvement is the device of Fig. 2.The results are shown in shown in following table 1:
The new and old device of table 1, prior art and the major economic indicators of cycle production process of the present invention contrast
The cycle production process of nigrosine provided by the present invention effectively utilizes the aniline steam of rectifying tower top and the gas-phase potential heat of water vapour on the one hand, low-pressure steam is utilized to drive lithium bromide chiller condenser, produce 7 degree of cold water for other workshops each refrigeration, the water of 12 degree is converted into after each workshop reacting kettle jacketing or interchanger heat exchange, the water cycle of generation 7 degree after lithium bromide chiller is driven to use through low-pressure steam again, the heat of rectifying tower tower top is comprehensively effectively utilized, and economic benefit is obvious.By rectifying tower top generation per hour 5310Kg low-pressure steam, replacing 0.6MPa steam driven lithium bromide chiller to produce 7 DEG C of cool water quantities is 500m
3/ h, supply workshop refrigeration needs.Steam expense per ton is by 200 yuan of calculating, and the whole year can steam saving expense about 7,650,000.On the other hand, compare with the device of improvement with old device, adopt cycle production process of the present invention to greatly reduce the consumption of recirculated water.
Claims (10)
1. a cycle production process for nigrosine, is characterized in that, described cycle production process comprises the steps:
1) aniline and oil of mirbane are carried out condensation reaction under catalyzer existent condition in condensation reaction still (16), obtain the nigrosine product containing excessive aniline;
2) under hydrochloric acid and hot water existent condition, by step 1) gained in acidification reaction still (17), carry out acidification reaction containing the nigrosine product of excessive aniline, then products obtained therefrom is obtained nigrosine product and containing aniline waste water by whizzer (18) is centrifugal;
3) by alkali lye with after being mixed by static mixer (7) containing aniline waste water, send into rectifying tower (3) tower top, steam directly enters at the bottom of rectifying tower (3) tower simultaneously, carry out stripping to the waste water containing aniline, the waste water produced at the bottom of rectifying tower (3) tower after stripping is decontaminated water factory and office reason after interchanger (8) heat exchange;
4) aniline of rectifying tower (3) tower top generation and the gas phase mixture of water enter lithium bromide chiller condenser (6) condensation; 12 DEG C of recirculated waters enter lithium bromide chiller condenser (6) simultaneously, the gas-phase potential heat produced by the gas phase mixture of aniline and water drives lithium bromide chiller condenser (6) to form 7 DEG C of recirculated waters for refrigeration, is converted into 12 DEG C of recirculated waters and enters lithium bromide chiller condenser (6) again and recycle after use of freezing;
5) gas phase mixture through lithium bromide chiller condenser (6) condensation becomes liquid phase mixture, condensation is carried out successively by the first condenser (41) and the second condenser (42), then enter decker (5) and carry out layering, upper strata aqueous phase contains a small amount of aniline, send back to static mixer (7) circulation carry out step 3) operation; Lower floor's aniline returns circulation in condensation reaction still (16) as the raw material of synthesis nigrosine and carry out step 1) operation.
2. cycle production process according to claim 1, is characterized in that, step 3) in be 3 ~ 8% containing the mass percentage content of aniline in aniline waste water, preferably 4%; The mass percentage content < 300ppm of the Aniline produced at the bottom of tower.
3. cycle production process according to claim 2, is characterized in that, step 4) in the temperature of gas phase mixture of aniline and water be 102 ~ 104 DEG C.
4. cycle production process according to claim 3, is characterized in that, step 5) in the temperature of liquid phase mixture be 95 ~ 100 DEG C.
5. the cycle production process according to claim 1-4 any one, it is characterized in that, step 3) described in liquid phase mixture after the first condenser (41) and the second condenser (42) are condensed to 20 ~ 25 DEG C, enter decker (5) successively and carry out layering.
6. cycle production process according to claim 5, is characterized in that, step 5) in lower floor aniline mutually in the mass percentage content of aniline be 94 ~ 98%.
7. the cycle production process according to claim 1-6 any one, it is characterized in that, described lithium bromide chiller condenser (6), described the first condenser (41) and the second condenser (42) are connected with cooling water supply pipe (9) and CWR (10) respectively.
8. cycle production process according to claim 7, is characterized in that, the downside of described rectifying tower (3) is provided with condensation-water drain.
9. cycle production process according to claim 1, is characterized in that, step 1) in the mass ratio of aniline and oil of mirbane be 4 ~ 6:1, the temperature of condensation reaction is 160 ~ 200 DEG C, and the time of condensation reaction is 4 ~ 6 hours, and described catalyzer is FeCl
3.
10. cycle production process according to claim 1, is characterized in that, step 2) described in the temperature of reaction of acidification reaction be 90 ~ 100 DEG C, the time of acidification reaction is 1 ~ 2 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510015951.0A CN104610173B (en) | 2015-01-13 | 2015-01-13 | A kind of cycle production process of nigrosine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510015951.0A CN104610173B (en) | 2015-01-13 | 2015-01-13 | A kind of cycle production process of nigrosine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104610173A true CN104610173A (en) | 2015-05-13 |
| CN104610173B CN104610173B (en) | 2017-03-29 |
Family
ID=53144859
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510015951.0A Active CN104610173B (en) | 2015-01-13 | 2015-01-13 | A kind of cycle production process of nigrosine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104610173B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112480709A (en) * | 2020-12-02 | 2021-03-12 | 丽水市大成新材料有限公司 | Production process of water-based velvet nigrosine |
| CN114149330A (en) * | 2021-12-06 | 2022-03-08 | 万华化学集团股份有限公司 | Energy-saving process for preparing aniline by nitrobenzene liquid-phase hydrogenation |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003022918A1 (en) * | 2001-09-06 | 2003-03-20 | Basf Aktiengesellschaft | Polyamide-based thermoplastic molding materials and single-piece and multiple-piece plastic shaped bodies made from said thermoplastic molding materials |
| WO2003091336A1 (en) * | 2002-04-26 | 2003-11-06 | Basf Aktiengesellschaft | Flame-resistant black thermoplastic moulded masses |
| CN101817791A (en) * | 2009-02-27 | 2010-09-01 | 严纪一 | Method for directly producing water soluble aniline black |
| CN101987816A (en) * | 2009-07-31 | 2011-03-23 | 宜兴市前成生物有限公司 | Waste heat comprehensive utilization device during the production process of fumaric acid |
-
2015
- 2015-01-13 CN CN201510015951.0A patent/CN104610173B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003022918A1 (en) * | 2001-09-06 | 2003-03-20 | Basf Aktiengesellschaft | Polyamide-based thermoplastic molding materials and single-piece and multiple-piece plastic shaped bodies made from said thermoplastic molding materials |
| WO2003091336A1 (en) * | 2002-04-26 | 2003-11-06 | Basf Aktiengesellschaft | Flame-resistant black thermoplastic moulded masses |
| CN101817791A (en) * | 2009-02-27 | 2010-09-01 | 严纪一 | Method for directly producing water soluble aniline black |
| CN101987816A (en) * | 2009-07-31 | 2011-03-23 | 宜兴市前成生物有限公司 | Waste heat comprehensive utilization device during the production process of fumaric acid |
Non-Patent Citations (1)
| Title |
|---|
| 王守恒，等: "醇溶苯胺黑生产废水中苯胺的回收", 《化学工业与技术》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112480709A (en) * | 2020-12-02 | 2021-03-12 | 丽水市大成新材料有限公司 | Production process of water-based velvet nigrosine |
| CN114149330A (en) * | 2021-12-06 | 2022-03-08 | 万华化学集团股份有限公司 | Energy-saving process for preparing aniline by nitrobenzene liquid-phase hydrogenation |
| CN114149330B (en) * | 2021-12-06 | 2023-10-17 | 万华化学集团股份有限公司 | Energy-saving process for preparing aniline by nitrobenzene liquid phase hydrogenation |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104610173B (en) | 2017-03-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102504567B (en) | Environment-friendly production method for permanent violet RL | |
| CN101817989B (en) | Method for preparing disperse blue 60 and homologues thereof | |
| CN104817481A (en) | Technological method for recovering DMSO from DMSO aqueous solution | |
| CN105461572A (en) | Clean technology for continuously synthesizing 2,4-dinitro-6-chloroaniline | |
| CN103145287A (en) | Method for recovering ammonia and synthesis gas from coking wastewater | |
| CN105967415A (en) | 2-naphthol high-salt and high-concentration organic matter wastewater recycling process and system | |
| CN104649898B (en) | A kind of solvent method continuous carbonization produces beta naphthal, the method and device of coproduction 2,3 acid | |
| CN105461571A (en) | Clean technology for continuously synthesizing 2,6-dichloro-p-nitroaniline | |
| CN104610173A (en) | Recycling production process for nigrosine | |
| CN105693560A (en) | Method for preparing energy-efficient H-acid | |
| CN104609491B (en) | A kind of recycling device of nigrosine factory effluent | |
| CN104671304B (en) | Comprehensive utilization method for gas-phase latent heat at top of rectifying tower | |
| CN103979577B (en) | A kind of coking desulfurization mixed salt extracts the method for sodium sulfocyanate | |
| CN212102640U (en) | System for preparing acetic anhydride by acetic acid cracking-ketene method | |
| CN202849288U (en) | DMF (dimethyl formamide) rectifying, recovering and recycling system | |
| CN204454953U (en) | A kind of circulation device for the production of nigrosine | |
| CN102350435A (en) | Novel process for treating indigo alkaline residue | |
| CN204454677U (en) | A kind of recycling device of nigrosine factory effluent | |
| CN204999762U (en) | Concentrated crystallization equipment of carnallite waste water | |
| CN204454954U (en) | The comprehensive utilization device of gas-phase potential heat in a kind of nigrosine production process | |
| CN109721035B (en) | Purification and concentration process of waste dilute sulfuric acid | |
| CN105254469A (en) | Chloroethane clean production process and device | |
| CN104610175B (en) | A kind of circulating device for producing nigrosine | |
| CN102276438A (en) | Production method of 1,5(1,8)-diphenoxy anthraquinone | |
| CN104610174B (en) | The comprehensive utilization device of gas-phase potential heat in a kind of nigrosine production process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP02 | Change in the address of a patent holder |
Address after: 266000 Qingdao, Shandong Province, Qingdao City, Pingdu City, New River ecological chemical technology industry base Jinshui Road No. 1 Patentee after: Qingdao Double-Peach Speciality Chemicals Group Co., Ltd. Address before: 266031 Shandong province Qingdao City, Yichang Road No. 31 Patentee before: Qingdao Double-Peach Speciality Chemicals Group Co., Ltd. |
|
| CP02 | Change in the address of a patent holder |